Process for converting hydrogen sulphide into sulphur



iant.

Nov. 19, 1935. B. H. LINCOLN 2,021,365

PROCESS FOR CONVERTING HYDROGEN SULPHIDE INTO SULPHUR Filed May 26, 1953 D/LUTE AL/(HL/ WATER TPEATEDG/LS 6/ SPRAY flasokee Assam/41025.0

7'0 .SULPHUE Ream/sky CONVERT/N6 I TOWER 6/45 czwm/M/ve yyawaw SOL/HIDE INVENTOR BY J6. if. v ATTORN a Patented Nev. 19, 1935 UNITED" STATES I PROCESS FOR. CONVERTING HYDROGEN sunrmm: m'ro SULPHUR,

Bert n. Iiincolm'Ponca City, Okla., assignor to Continental Oil Company, Ponca City, Okla., a corporation of Delaware Application May 26, 1933, Serial No. 673,021 7 1 Claim.

My invention relates to a process for converting hydrogen sulphide into sulphur,

Hydrogen sulphide is a common constituent of most hydrocarbongases. The percentage of hydrogen sulphide in hydrocarbon gases as obtained in the production of petroleum will vary depending upon the-producing field andthe type of crude. The percentage of hydrogen sulphide may'be very large and reach an amount of by volume 10 or more. In cracking heavy hydrocarbons into lighter hydrocarbons the mercaptans and/or other sulphur compounds in the heavy hydrocarbons are in part broken down. with hydrogen sulphide resulting. The hydrogen sulphide so produced contaminates the cracked gas coming from the cracking unit. In some cases hydrogen sulphide is released in the ordinary distillation of petroleum hydrocarbons either due to the heat converting the sulphur compound into hydrogen sulphide or due to the reduced solubility of hydrogen sulphide in the hydrocarbon oil at elevated temperature.

Hydrogen sulphide in hydrocarbon gases is as a rule a very objectionable constituent. It is a very active corrosive agent and has'marked corrosive effect on certain types of metals'encountered in the transportation and use of hydrocarbon gases. When the percentage by volume of 80 hydrogen sulphide increases above a very low figure it makes the entire bodyof gaseous hydrocarbons dangerous due to its poisonous action. There are large volumes of naturalhydrocarbon gases and gases formed during the cracking of 35 the hydrocarbons that cannot be marketed for domestic consumption because of the high hydrogen sulphide content.

The-object of my present invention is to provide a method and apparatus'for the removal of 40 hydrogen sulphide from gases such as hydrocarbon gases. Another object of my invention is to provide an economical method for the removal of hydrogen sulphide from hydrocarbon gases tion therewith, discloses a schematic view of one 5g apparatus capable 'of carrying: out my invention.

' troleum coke.

without diluting thehydrogen sulphide free gas When sulphurous acid contacts with hydrogen sulphide the following reaction occurs:

A tank I is provided for the storage of sulphur: 5

ous acid which may be obtained by contacting sulphur dioxide with water. 'A pump 2 is adapted to pump sulphurous acid through line 3 and through branch line 4 .to manifolds 5 and 6. Lines 1 and 8 extend from manifold 5 to tower I0. 10 Lines H and i2 extend from manifold 6 to tower I have discovered that a reaction between hydrogen sulphide which may be contained in a hydrocarbon gas, and sulphurous acid may be 15 more readily accomplished in ,a tower packed with inert or activated substances which act either to give an increased contacting surface or a, catalytic action. I

A substance which I have found particularly 20 suitable as a catalyst is activated carbon from any source, or obtained from de-volatilized pe- The towers l0 and H are filled with the packing material N5, of a nature just described. Valves l! and [8 control lines I and 8 26 so that sulphurous acid may be introduced into the tower through either lines I or 8 as desired. Valves l9 and 20 perform the same function with respect to tower I4. The gas containing hydrogen sulphide from any suitable source is introduced into line 22 which'is controlled by valve 23 and passes through lines 24 and 25 to towers l0 and 14 respectively. If the sulphurous acid be delivered into the bottom of the towers, the gas containing hydrogen sulphide and the sulphurous acid will flow upwardly in parallel through towers i4 and It. It is my intention, however,- that only one of towers IE or I 4 be in use at one time so that, when the catalyst or inert material in one of the towers becomes contaminated by the collection of free sulphur, which may be precipitated, the other tower may be put in stream and the tower which has become contaminated be subjected to cleaning. This is done by means of steam which is introduced to line 30. I use ,high pressure steam opening manhole 3! to allow for cleaning out of the sulphur at the base of the tower. Manholes 32 are provided in the upper portion of the tower for the introduction of the contact material.

If a relatively strong solutionof sulphurous acid 60 is used in my process, I find it advisable to deliver the sulphurous acid to the middle portion of the tower to allow contact of any sulphur dioxide which may be released in the presence of the gas to react with the hydrogen sulphide which is contained in the gas. If the relatively strong sulphurous acid be delivered into the top of the tower, free sulphur dioxide will be blown from the solution before it has time to contact with the hydrogen sulphide. v

The treated gas and sulphurous acid leaves the towers through lines 40 and passes into line 4 l to separator 42. In the separator, the liquid containing elemental sulphur in suspension is withdrawn through line 43. I provide towers i0 and I4 with lines 44 and 45 leadingfrom the lowest point thereof. These lines pass into the main 4. from'which the liquid containing the sulphur in suspension is pumped by pump 41 to suiphurrecovery. The sulphur may be recovered by settling, centrifuging, or filtering. It may be recovered either in the finely divided form being precipitated or may be melted; and used'in cores. The gases will be found to be substantially free of hydrogen sulphide. If traces of hydrogen sulphide are still present, the gas leaving the separator through line I may be passed into the baflle tower 5i containing baifle plates II. A branch line 53 'is connected to a sulphurous acid line 4 and may be introduced into tower 8| so'that the gas coming from line will pass counter-current thereto. This tower is likewise provided with a line 54 for drawing of! the sulphurous acid and/or water containing elemental sulphur in suspension. This line leads to line 40 as can be readily seen by reference to the drawing. A cleanout manhole 55 is provided. The treated gas is drawn from tower II through line I. and passes into baiiie tower 51 countercurrent to a spray of either water or a dilute alkaline solution to neutralize any traces of sulphurous acid which may be present in the gas. Thesulphur water or alkali'is introduced through line to spray head.

lit. The sulphur .water is withdrawn at the bottom of tower 51 to line 00 and the treated gas is withdrawn through line 8|.

Any sulphur deposited in the lines or other equipment may beremoved by the solvent action of carbon diosulphide or ammonium sulphide or x ly reduced.

be removed by blowing through with high pressure steam. Suitable manholes l2 and- 03 are forcleaning out separator 42 and tower through a tower-packed with glass beads through which a solution of sulphurous acid was percolated. The resulting gas'contained 900 8 of hydrogen sulphide per 100 cubic feet. with a slower rate oi' flow of gas containing hydrogen or an increased quantity of sulphurous acid or with better contact surface, the hydrogen sulphide content of the treated gas could have been great- Asanother example of my process, a-tower packed with a commercially availableactivated cocoanut charcoal was used as the contacting surface. A gas containing 3000 grains of hydrogen sulphide per cubic feet' was passed up through the tower and a solution of sulphurousv acid percolated from the top of the tower. The gas resulting from this operation contained approximately 500 grains of hydrogen sulphide per 100 cubic feet. 7

The equipment should be so designed to operate under pressure. This is necessary since the gas to be treated Temperatures up to the vaporization temperature 5 of sulphurous acid (water) under the pressu employed may be used.

By controlling the rate of flow the concentration of sulphurous acid used and the amount of contact surface, it is possible to reduce'the hydrogen sulphide content of a gas to 25 grains per 100 cubic feet or lower. 1

I have found that the desirable characteristics of my process are not obtained by the use of dry sulphur dioxide as a substitute for the sulphurous l5 acid used. The water solution of'sulphur dioxide (sulphurous acid) gives a much'more rapid reac-, tion than the dry sulphur dioxide.

Another desirable characteristic of sulphur dioxide water solution (sulphurous acid) not ob- 20 tainable with dry sulphur dioxide is the fact that the water solution tends to wash the sulphur pre- 'cipitated by the reaction from the reaction chamber and gives a convenient means of accumulating and collecting the sulphur formed by the re- 25 action. The reaction rate with sulphurous'acid being so much greater, allows the design of apps-'- ratus for the handling of any given volume of hydrogen sulphide containing gas to be made with much smaller equipment than is possible when so remaining in the treated gas is easily removed 35:

bis. water wash or a dilute alkaliwash. Water may be employed since the solubility of sulphur igen sulphide per 100 cubic feet was passed.

dioxide in water provides a very economical and convenient means of removing the sulphur dioxide. When an extremely pure gas is required. a 40 small and should provide a very economical meth- 4s 0d of obtaining a pure hydrocarbon gas free of sulphur dioxide and hydrogen sulphide.

It will be understood that certain features and sub-combinations are of utility and may be employed without reference to other features and 50 sub-combinations. This is contemplated by and is" within the scope of my claim. It is further vated carbon. whereby to convert a portion of the hydrogensulphide into water-and elemental sulphur, separating the gas from the products formed by the reaction, then passing the gas eountercurrent to sulphurous acid to convert the remaining hydrogen sulphide into water and sul- 70 phur and then-washing the-treated sas.

BERT I-l. mucous. 

